The Enantioselective Construction of Tetracyclic Diterpene Skeletons with Friedel-Crafts Alkylation and Palladium-catalyzed Cycloalkenylation Reactions

Due to the profound extent to which natural products inspire medicinal chemists in drug discovery, there is demand for innovative syntheses of these often complex materials. This article describes the synthesis of tricarbocyclic natural product architectures through an extension of the enantioselective Birch-Cope sequence with intramolecular Friedel-Crafts alkylation reactions. Additionally, palladium-catalyzed enol silane cycloalkenylation of the tricarbocyclic structures afforded the challenging bicyclo[3.2.1]octane C/D ring system found in the gibberellins and the ent-kauranes, two natural products with diverse medicinal value. In the case of the ent-kaurane derivative, an unprecedented alkene rearrangement converted four alkene isomers to one final product

Geochemical Characteristics of Granitoids (Ho Gneiss) from the Pan – African Dahomeyide Belt, Southeastern, Ghana: Implications for Petrogenesis and Tectonic Setting

The Pan-African Dahomeyide belt exposed in Southeastern, Ghana, consist of granitoid gneisses locally known as Ho gneiss. These rocks are thought to be part of the West African Craton (WAC) which was reworked during the Pan-African Orogeny, and may be time equivalent with the Kara gneisses. Petrographical and whole rock geochemical analyses have been used to evaluate the characteristics, petrogenesis and mode of emplacement of the granitoids. The new data reasonably suggest that the Ho gneiss consist mainly of biotite augen gneisses of both mafic and felsic rock suites. Geochemically, these rocks show tonalitic to quartz monzonite but mainly granodiorites affinities. They are metaluminous to weakly peraluminous, I-type, magnesian to ferroan and calcic to alkali calcic. With these varying features, the granitoids mimic mantle derived magma source which mixed or mingled with crustally derived melt. The rocks display varying REEs and trace elements patterns but, their LREEs and LILE enrichment with  the noticeable enrichment in Rb, Ba, K and especially Pb and negative Ti, Ta, Nb observed among majority of the samples are typical signature of ‘‘arc rocks’’ or continental crustal materials. Their incompatible trace element ratios, such as Th/U (1.07 – 13.87), K/Rb (272 – 574.47), Th/Yb (0.79 – 15.09), Ta/Yb (0.25 -0.64 ), Ce/Pb (mainly 1.62 – 7.88 ) and high Ba/Nb (19.55 – 314.17, with TA = 1565.00), are similar to those of the continental crust. The rocks are characterised by subduction related Sr/Y content (< 100), except sample MA8 that shows high concentration of Sr/Y (227.71). The magnesian affinity reflects relatively hydrous, oxidizing source which is consistent with origins that are broadly subduction related. Their high – K nature also points to an important petrogenetic role of remelting and differentiation of arc – accretionary complex crust. These geochemical signatures are likely to be related to metasomatism of the sub – continental lithospheric mantle via crustal recycling. In conclusion, the granitoids may have from melting of igneous source in a subduction related environment. Keywords: Pan-African belt, Dahomeyide, Southeastern Ghana, Ho gneisses, Geochemistry, petrogenesi